Phosphorus containing compounds

ABSTRACT

IN WHICH R1 is alkyl or alkoxy, R2 is hydrogen or alkyl, R3 is alkyl, R4 is alkyl, R5 is methyl or -CH2COOCH3 and X is oxygen or sulfur and their use as insecticides and acaricides.   The compounds of this invention are those having the formula

United States Patent 1 Gutman 1 3,760,040 Sept. 18, 1973 PHOSPl-IORUSCONTAINING COMPOUNDS [75] Inventor: Arnold D. Gutman, Berkeley, Calif.

[73] Assignee: Staulier Chemical Company, New

York, N.Y.

[22] Filed: Apr. 24, 1972 [21] Appl. No.: 247,172

[52] US. Cl 260/941, 260/942, 260/973,

260/984, 424/212 [51] Int. Cl C07f 9/08, C07f 9/20, C07f 9/24 [58] Fieldof Search 260/941, 942, 944

[56] References Cited UNITED STATES PATENTS 8/1972 Gutman ..260/9441/1973 Lutzetal Primary Examiner-Lewis Gotts Assistant Examiner-RichardL. Raymond Attorney-Edwin H. Baker et al.

57 ABSTRACT The compounds of this invention are those having the formula10 Claims, No Drawings PHOSPHORUS CONTAINING COMPOUNDS This inventionrelates to certain novel phosphorus containing chemical compounds andtheir use as insecticides and acaricides.

The compounds of this invention are those having the formula in which Ris alkyl having one to four carbon atoms or alkoxy having one to fourcarbon atoms, R is hydrogen or alkyl having one to six carbon atoms,preferably one to four carbon atoms, R is alkyl having one to six carbonatoms, preferably one to four carbon atoms, R is alkyl having one tofour carbon atoms, R is methyl or CH COOCH and X is oxygen or sulfur.

The compounds of the present invention can be prepared according to thefollowing reactions:

Reaction l is carried out by reacting preferably equal mole amounts ofthe two reactants. If an excess of either-reactant is used, the reactionstill proceeds but purity is reduced. The reactants can be combined inany manner but preferably the reactants are mixed together in a solventsuch as benzene, preferably with stirring'in the presence of an acidacceptable such as triethylamine. The temperature of the reaction is notcritical, however, better yields are obtained by keeping the reactantsat a temperature below 30C for a time sufficient to allow completion ofthe reaction. The resulting product can be recovered from the reactionmixture by conventional means such as by washing the benzene mixturewith water. The benzene is dried with anhydrous Mg'SO; and thenevaporated to yield the desired product. A more purified product can beobtained by distilling in vacuo.

Preferably. Reaction ll is carried out by reacting an excess of ammoniawith the other reactant. The reactants can be combined in any desiredmanner, but preferably, the reaction is run in a solvent such as diethylether at a temperature below 30C. The resulting product is recovered andpurified by standard procedure. For'example, the resulting product canbe recovered and purified from the reaction mixture by washing withwater. The ether phase is dried with anhydrous MgSO, and evaporated toyield the purified product.

Reaction III utilized as a reactant the product of Reaction ll. In theprocess, the reaction is carried out by reacting preferably about equalmole amounts of the reactants. An excess of the ortho ester reactant canbe used. Although the reactants can be combined in any desired manner,it is preferred to mix the reactants in a solution of acetonitrilesolvent in the presence of alcoholic HCl. Preferably, the reaction iscarried out at a temperature about 100C. The reaction product isrecovered by conventional means such as by stripping in vacuo at 40C and0.01 millimeter pressure to yield the purified product.

Preparation of the compounds of this invention is illustrated in thefollowing examples:

EXAMPLE I O-( 2-carbomethoxyl -methylvinyl)methylphosphonothiochloridate s CH3 CH3FOC=CHCOOCH3 149 grams (1.0 mole)of methylphosphonothioic dichloride, 1 16 grams (1.0 mole) of methylacetoacetate and 750. milliliters of benzene are charged into a twoliter 3 neck flask fitted with a stirrer, thermometer and droppingfunnel. The solution is cooled in an ice bath to 10C. To the rapidlystirring solution is added 101 grams (1.0 mole) of 'triethylamine atsuch a rate that the temperature does not exceed 30C. After the additionis complete the reaction mass is stirred at room temperature for 1 hourand then at 35-40C for two hours. When thetpl-l of the reaction massbecomes acidic, it is cooled to 15C and is washed with two 350milliliter portions of water. The benzene phase is then dried withanhydrous MgSO and evaporated. The residue was distilled in vacuo togive 103.7 grams of the desired intermediate product. B.P. 83-85C/EXAMPLE ll O-(carbomethoxy-l-methylvinyl) methylphosphonothioamidate fiCH3 CHQPOC=CHCOOCH.:

hydrous MgSO, and evaporated to yield 41.0 grams of the desiredintermediate product. N -1.5301.

EXAMPLE [[1 O-(carbomethoxy-l-methylvinyl) N- 5 ethoxyformylidene)methylphosphonothioamidate 5 (Ha CH;,II"OCHCOOCH;I

1L=COC Ha .8.0 grams (0.0395 mole) of the reaction product of Example11, 14.8 grams (0.1 mole) of triethylorthoformate, 50 milliliters ofacetonitrile, and 0.2 milliliters of alcoholic 1-1C1 are combined in a250 milliliter round bottom flask. Themixture is heated on a steam bathuntil the pot temperature reaches 100C. The reaction mass is thenstripped in vacuo at 40C and 0.01 millimeter to yield 9.0 grams of thedesired compound. N -l.5097.

EXAMPLE IV O-(2-carbomethoxy-1-methy1viny1)O-ethylphosphorothiochloridate S CH1;

C H -,OPOC=CHCOOCH:1

42 grams (0.2 mole) of 25 percent sodium methoxide solution and 23.2grams (0.2 mole) of methyl acetoacetate are combined in a 500 milliliterround bottom flask. After a slight exotherm subsides, the mixture isheated on a steam bath for 15 minutes. The reaction mass is thenstripped in vacuo. The residue is titrated with 250 milliliters ofbenzene, and the reaction mass is again stripped in vacuo. The residueis dissolved in 400 milliliters of tetrahydrofuran.

35.8 grams (0.2 mole) of ethylphosphorothioic dichloride and 150milliliters of tetrahydrofuran are combined in a one liter 3 neck flaskfitted with a stirrer, thermometer and dropping funnel. The solution isstirred and cooled in an ice bath to 5C, and the tetrawashed with three300 milliliter portions of ice water.

The ether phase is dried with anhydrous MgSO. and evaporated in vacuo at100C and 0.1 millimeter to yield 30 grams of the desired intermediateproduct. N 1.498O.

EXAMPLE V O-(Z-carbomethoxy-1-methy1viny1) O-ethylphosphorothioamidate sCH3 30.0 grams (0.116 mole) of the reaction product of Example IV iscombined with 250 milliliters of diethylether in a 500 milliliterErlenmeyer flask. The solution is cooled in an ice bath and is saturatedwith anhydrous ammonia gas. The reaction mass is then transferred to aseparatory funnel and washed with two 200 milliliter portions of water.The ether phase is dried with anhydrous MgSO. and evaporated to yield24.1

grams of the desired product. N 1.5082.

EXAMPLE V1 O-( 2-carbomethoxy- 1 -methylviny1)N-(aethoxypropylidene)O-ethylphosphorothioamidate 5.0 grams (0.0208 mole) of the reactionproduct of Example V, 8.8 grams (0.05 mole) of triethylorthopropionate,milliliters of acetonitrile, and 0.2 milliliters of alcoholic HCl arecombined in a 250 milliliter round bottom flask. The mixture is heatedon a steam bath until the pot temperature reaches 100C. The reactionmass is then stripped in vacuo at C and 0.01 millimeter to yield 5.5grams of the desired compound. N -1.4943.

The following is a Table of certain selected compounds that arepreparable according to the procedure described hereto. Compound numbersare assigned to each compound and are used throughout the remain- 50 derof theapplication.

v TABLE 1 1 i R'POC==CHCOOR Compound 2 S CzHs C- -H. CgHr, CH1; CH1.5065 3 S C2H5 H CH3 CH3 CH3 1.5154

4 S z s H CzHr, CH;. CH 1.5072

5 S CH H C- H CH CH 1.5097

6 5 H1 CH; CzHr. CH3 CH3 1.5022

7 5 CH3 C2 CgHr, CH3 CH3 1.4906

3 3 1; 'H CH CH" CH 1.5176

9 5 BO H C. CH3 CH. 1.4980

TABLE i-cominhli l T RPOC=CHCOOR N=COR Compound 1 Number X R R R" R RN,,="

S EtO CH3 CzHs CH CH 1.5029 11 S EtO C2H5 C2H5 CH; CH 1.4943 12 O HO H CH5 CH3 CH3 1.4712 13 0 BO CH3 C2115 CH3 CH3 1.4740 14 O HO C H CQHS CHCH 1.4658 15 S CzHs H CzHs CH CH COOCH 1.5037 16 S CzH; C H5 C H CH CHCOOCH 1.4887 17 S C H H CzHs C H5 CH 1.4980 is s 02H. H g mcri. c25 cua1.4710 19 S CgHs (CH2)3CH3 CH3 CzHs CH3 1.4924 20 S CzH5 CH3 C2H5 C-gHsCH 1.4987 2| S I CzHs CzHs CzHs C2; CH3 [.4820 22 S C l-l H CH C H CH1.5078

lnsecticidal Evaluation Tests 7..'Tobac co Budworm (TBW) Heliothisvirescens 8. Mosquito (MOS) Culex pipiens quinquefasciates The Housefly(HF) was used in evaulation tests of selected compounds as insecticidesby the following procedure. A stock solution containing 100 ug/rnl ofthe toxicant in "an appropriate solvent was prepared. Aliquots of thissolution were combined with l milliliter of an acetone-peanut oilsolution in an aluminum dish and allowed to dry. The aliquots were thereto achieve desired toxicant concentration ranging from 100 ug per dishto that at which 50 percent mortality was attained. The dishes wereplaced in a circular cardboard cage, closed on'the bottom withcellophane and covered on top with cloth netting. Twenty-five femalehouseflies, three to five days old, wereintroducedinto the cage and thepercent mortality was recorded after 48 hours. The LD-50 values areexpressed in terms of ug per-2 5 female flies. The results of theseinsecticidal evaluation tests are given in Table 11- under l-lF 1n theGerman Cockroach (GR) tests, 10, one-month old nymphs were placed inseparate circular cardboard 'cage's sealed on one end with-cellophaneand covered by "a cloth netting on the other. Aliquots of the toxicants,dissolved in an appropriate solvent, were diluted in water containing0.002 percent of a wetting agent, Sponto 221, (a polyoxyether ofalkylated phenols blended with organic sulfona tes). Test concentrationsranged from 0.1 percent downward to that at which 50 percent mortalitywas obtained. Each of the aqueous suspensions of the candidate compoundswas sprayed onto the insects through the cloth'netting 'by means of ahand-spray ,gun. 'Pe'rcent'mortality in each case was recorded after 72hours, and the LD- 50 values, expressed as percent of toxicant in theaqueous spray, were recorded. These values are reported under the columnGR" in Table 11.

The Lygus Bug (LB), Lygus hesperus, was tested similarly as the GermanCockroach. The caged insects were sprayed with the candidate compoundsat concentrations ranging from 0.05 percent downward to that at which 50percent mortality was obtained. After 24 and 72 hours, counts were madeto determine living and dead insects. The LD-SO (percent) values werecalculated. These values are reported under the column LB in Table 11.

The insect species Black Bean Aphid (BA), Aphis fabae, Scop.) was alsoemployed in the test for insecticidal activity. Yound nasturtium(Tropaeolum sp.)

.plant s, approximately 2 to 3 inches tall, were used as the host plantsfor the Bean Aphid. The host plant was infested with approximately 50-75of the aphids. The test chemical was dissolved in acetone, added't'owater which contained a small amount of Sponto 221, an emulsifyingagent. The solution was applied as a spray to the infested plants.Concentrations ranged from 0.05 percent downward until an LD-SO valuewas achieved. These results are given in Table 11 under the Column Fortesting the'Salt-marsh Caterpillar, test solutions were prepared in anidentical manner and at concentrations the same as for the GermanCockroach, above. Sections of bitter dock, Rumex obtusifolus, leaves,-l- -1.5 inches'in length were immersed in the test solutions forglO to15 seconds and placed on a wire screen to dry. The dried leaf was placedon a moistened piece of filter-paperin a Petri dish and infested withfive third-instar larvae. Mortality of the larvae was recorded after 72hours, and the LD-50 values are expressed as percent active ingredientin the aqueous suspension.

in the insecticidal test employing Beet Armyworm, test solutions wereprepared in the same manner and at the same concentrations as those usedfor German Cockroach test. Sections of Romaine lettuce ('Latuca sativa)were utilized as the host plant. The lettuce leaves were immersed inthetest solution for.-l0-'l5 seconds and placed on a wire screen to dry.The dried leaf was placed on a moistened piece of filter paper in aPetri dish and infested with five third-instar larvae. Mortality of thelarvae was recorded after 72 hours. The LD-50 values are expressed aspercent active ingredient in the aqueous suspensions. These values arereported under Column BAW in Table ll.

The test on Tobacco Budworm [Heliothis virescens (F is the same as theone for the Salt-marsh Caterpillar except that leaves of Romaine lettuce(Latuca sativa) are utilized as the host plant rather than bitter clock.The LD-50 values are expressed as percent active ingredients in theaqueous suspension and are reported under the column TBW in Table II.

In the Mosquito Bioassay one hundred milliliters of an aqueous solutionof the candidate compound, at an initial concentration of 0.5 p.p.m.,are placed in a 6 ounce wax paper cup. Ten late third or early fourthinstar larvae of the mosquito Culex pipiens quinquefasciates are placedin each cup and the cups are stored at 70F for three days. At the end ofthis time, mortality counts are made. Compounds which are active at 0.5p.p.m. are retested at progressively lower concentrations until an LD-50value is determined. These results are given in Table 11 under thecolumn MOS.

Acaricidal Evaluation Test The two-spotted mite (28M), Tetranychusurticae (Koch), was employed in tests for miticides. Young pinto beanplants or lima bean plants (Phaseolus sp.) in the primary leaf stagewere used as the host plants. The young pinto bean plants were infestedwith about 100 mites of various ages. Dispersions of candidate materialswere prepared by dissolving 0.1 gram in milliliters of a suitablesolvent, usually acetone. Aliquots of the toxicant solutions weresuspended in water containing 0.002 percent v/v Sponto 221,polyoxyethylene ether sorbitan monolaurate, an emulsifying agent, theamount of water being sufficient to give concentrations of activeingredient ranging from 0.05 percent to that at which 50 percentmortality was obtained. The test suspensions were then sprayed on theinfested plants to Systemic Evaluation Test This test evaluates the rootabsorption and upward 10 translocation of the candidate systemiccompound. The

two-spotted mite (ZSM) Tetranychus urticae, (Koch) .and the Bean Aphid(BA) Aphis fabae (Scop.) were employed in the test for systemicactivity.

Young pinto bean plants in the primary leaf stage were used as hostplants for the two-spotted mite. The

pinto bean plants were placed in bottles containing 200 milliliters ofthe test solution and held in place with cotton plugs. Only the rootswere immersed. The test solutions were prepared by dissolving thecompounds to be tested in a suitable solvent, usually acetone, and thendiluting with distilled water. The final acetone concentration neverexceeded about 1 percent. The toxicants were initially tested at aconcentration of 10 parts per million (p.p.m.). Immediately after thehost plant was placed in the test solution it was infested with the testspecies. Mortalities were determined after seven days.

Young nasturtium plants were used as the host plants for the Bean Aphid.The host plants were transplanted into one pound of soil that had beentreated with the candidate compound. Immediately after planting in thetreated soil the plants were infested with aphids. Concentrations oftoxicant in the soil ranged from 10 ppm. per pound of soil downwarduntil an LD-50 value was obtained. Mortality was recorded after 72hours.

The percentage of kill of each test species was determined by comparisonwith control plants placed in distilled water or untreated soil. TheLD-50 values were calculated. These systemic test results are reportedin Table 11 under the columns BA-Sys" and 2SM-Sys.

TABLE 11 LD- VALUES Compound HF GR LB BA SYS SMC BAW TBW PE EGGS SYS MOSNumber (percent) (percent) (percent) (percent) (p.p.m.) (percent)(percent) (percent) (percent) (percent) (p.p.m.) (p.p.m.)

the point of run off. After seven days, mortalities of postembroyonicand ovicidal forms were determined.

As those in the art are well aware, various techniques are available forincorporating the active component or toxicant in suitable pesticidalcompositions. Thus, the pesticidal sompositions can be convenientlyprepared in the form of liquid or solids, the latter preferably ashomogeneous free-flowing dusts commonly formulated by admixing theactive component with finely divided solids or carriers as examplifiedby talc, natural clays, diatomaceous earth, various flours, such aswalnut shell, sheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersionof the toxicant in a liquid media, although it may be convenient todissolve the toxicant directly in a solvent such as kerosene, fuel oil,xylene, alkylated naphthalenes or the like and use such organicsolutions directly. However, the more common procedure is to employdispersions of the toxicant in an aqueous media and such compositionsmay be produced by forming a concentrated solution of the toxicant in asuitable organic solvent followed by dispersion in water, usually withthe aid of surface active agents. The latter, which may be the anionic,cationic, or nonionic types, are exemplified by sodium stearate,potassium oleate and other alkaline metal soaps and detergents such assodium lauryl sulfate, sodium naphthalene sulfonate, sodium alkylnaphthalane, sulfonate, methyl cellulose, fatty alcohol ethers,polyglycol fatty acid esters and other polyoxyethylene surface activeagents. The proportion of these agents commonly comprises l-15 percentby weight of the pesticidal compositions although the proportion is notcritical and may be varied to suit any particular situation.

I claim:

1. The compound having the formula in which R is alkyl having one tofour carbon atoms or alkoxy having one to four carbon atoms, R ishydrogen or alkyl having one to six carbon atoms, R is alkyl having oneto six carbon atoms, R is alkyl having one to four carbon atoms, R ismethyl or CH COOCH and X is oxygen or sulfur.

2. The compounds of claim 1 in which R is alkyl having one to fourcarbon atoms, R is alkyl having one to four carbon atoms, R is alkylhaving one to four carbon atoms, R is alkyl having one to four carbonatoms, R is methyl and X is sulfur.

- 3. The compounds of claim 1 in which R is alkoxy having one to fourcarbon atoms, R is alkyl having one to four carbon atoms, R is alkylhaving one to four carbon atoms, R is alkyl having one to four carbonatoms,

R is methyl and X is sulfur.

4. The compounds of claim 1 in which R is alkyl having one to fourcarbon atoms, R is hydrogen having one to four carbon atoms, R is alkylhaving one to four carbon atoms, R is alkyl having one to four carbonatoms, R is methyl and X is sulfur.

5. The compounds of claim 1 in which R is alkoxy having one to fourcarbon atoms, R is hydrogen having one to four carbon atoms, R is alkylhaving one to four carbon atoms, R is alkyl having one to four carbonatoms, R is methyl and X is sulfur.

6. The compound of claim 1 in which R is ethyl, R is methyl, R is ethyl,R is methyl, R is methyl and X is sulfur.

7. The compounds of claim 1 in which R, R and R are ethyl, R and R aremethyl and X is sulfur.

8. The compounds of claim 1 in which R is ethoxy, R and R are ethyl, Rand R are methyl and X is sulfur.

9. The compounds of claim 1 in which R is ethyl, R is hydrogen, R and Rare ethyl, R is methyl and X is sulfur.

10. The compounds of claim 1 in which R is methyl, R and R are ethyl, Rand R are methyl and X is sulfur.

2. The compounds of claim 1 in which R1 is alkyl having one to fourcarbon atoms, R2 is alkyl having one to four carbon atoms, R3 is alkylhaving one to four carbon atoms, R4 is alkyl having one to four carbonatoms, R5 is methyl and X is sulfur.
 3. The compounds of claim 1 inwhich R1 is alkoxy having one to four carbon atoms, R2 is alkyl havingone to four carbon atoms, R3 is alkyl having one to four carbon atoms,R4 is alkyl having one to four carbon atoms, R5 is methyl and X issulfur.
 4. The compounds of claim 1 in which R1 is alkyl having one tofour carbon atoms, R2 is hydrogen having one to four carbon atoms, R3 isalkyl having one to four carbon atoms, R4 is alkyl having one to fourcarbon atoms, R5 is methyl and X is sulfur.
 5. The compounds of claim 1in which R1 is alkoxy having one to four carbon atoms, R2 is hydrogenhaving one to four carbon atoms, R3 is alkyl having one to four carbonatoms, R4 is alkyl having one to four carbon atoms, R5 is methyl and Xis sulfur.
 6. The compound of claim 1 in which R1 is ethyl, R2 ismethyl, R3 is ethyl, R4 is methyl, R5 is methyl and X is sulfur.
 7. Thecompounds of claim 1 in which R1, R2 and R3 are ethyl, R4 and R5 aremethyl and X is sulfur.
 8. The compounds of claim 1 in which R1 isethoxy, R2 and R3 are ethyl, R4 and R5 are methyl and X is sulfur. 9.The compounds of claim 1 in which R1 is ethyl, R2 is hydrogen, R3 and R4are ethyl, R5 is methyl and X is sulfur.
 10. The compounds of claim 1 inwhich R1 is methyl, R2 and R3 are ethyl, R4 and R5 are methyl and X issulfur.